Pesticidal petroleum composition and use thereof



PESTICIDAL PETROLEUM COMPOSITION USE THEREOF Franklin (I. Nelson, Roselle, N.J., and George W. Fiero, Port Chester, N.Y., assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Application January 18, 1955 Serial No. 482,672

19 Claims. (Cl. 16728) This invention relates to new pesticidal compositions which contain a virgin heavy aromatic naphtha fraction, or an aromatic kerosene or light gas oil fraction, as an essential ingredient thereof. The invention also relates to the use of such compositions in killing houseflies and other insects.

The use of various aromatic petroleum oils as mild pesticides or insecticides is well known in the art, and their insecticidal activity has heretofore been ascribed essentially to their aromatic nature. For instance, methyl substituted naphthalenes have been recognized some years ago as valuable ingredients of insecticidal compositions. Furthermore, it has also been suggested that suitable fractions containing the desired active aromatic ingredients could be obtained from coal tar or especially by hydroforming or high temperature cracking of appropriate petroleum oils.

It has now been discovered, however, that virgin aromatic petroleum fractions boiling in the range of about 300 to 625 F., and especially between 450 or 460 and 535 F., and containing about 80 to 95 percent aromatics have insecticidal properties so unexepectedly superior to anything previously observed that a difference in kind is clearly involved. This diiference is particularly surprising since the novel virgin material has proved greatly superior to seemingly similar fractions isolated from cracked, hydroformed or other non-virgin aromatic petroleum fractions which have been heretofore considered especially valuable in the insecticide art. While no definite explanation of this difference has been established, and it is certainly not intended to-limit this invention to any particular theory, the astonishing hypothesis is nevertheless proposed herewith that perhaps the relatively small amount of the specific paraflinic or non-aromatic hydrocarbons present in the novel insecticidal compositions, or possibly a critically difierent structure of some specific aromatic compound or compounds present, exerts an entirely unexpected synergistic parasiticidal elfect in conjunction with the other aromatics normally present in non-virgin petroleum fractions of the same boiling range. Whatever this highly active virgin constitutent may be, it seems that it is only too readily destroyed when a fraction containing it is subjected to such conventional conversions as thermal or catalytic cracking, reforming, hydroforming, etc.

In accordance with this invention the virgin aromatic fractions of the type described may be used as insecticides without the addition of other toxicants since,unlike previously known petroleum products, the present virgin fractions are not only outstanding paralytic. or knockdown agents, but are in and by themselves also excellent killers or toxicants. However, where the insecticide is intended particularly for residual use, especially outstanding products can be formulated by blending the novel virgin aromatic fractions with a minor amount of supplemental killing agents such as DDT (dichlorodiphenyl-trichloroethane) or other'conventional toxicants. Of course, insecticidal sprays formulated. from States Patent 2,898,263 Ice Patented Aug. 4, 1959 the novel pesticidal compositions may also include relatively inert solvents such as deodorized kerosene'and,

where aerosols or pressurized sprays are wanted, also volatile propellants such as methyl chloride,'trichloro 5 fluoromethane, dichlorotetrafluoroethane, octafluoropropane and other low-melting, low-boiling halogenated C -C alkanes; or they may be used as aqueous emulsuch spray compositions contain at least about 10 percent of the novel virgin aromatic fraction.

Especially effective virgin aromatic concentrates have. been prepared from aromatic Texas Gulf crudes such as Tomball or Conroe crudes which generally'contain in excess of 20 percent of aromatics and a sulfur content of well under 1 percent, usually under 0.05 percent- However, indications are thatsimilarly useful materials can be obtained from any other crudes available, including paraifinic as well as naphthenic type crudes with comparatively minor variations in insecticidal activity from case to case. Of course, the yield of the desired virgin aromatic concentrate will differ considerably, depending on the aromaticity of the particular crude used. On the other hand, once a concentrate of proper aromatics content and boiling range is isolated, its specific origin-seems to have only a comparatively minor elfect" on its insecticidal activity, though the product from the oxide. However, other known solvent systems such as phenol, ammonia, furfural-furfuraldehyde, dichloroethyl ether and the like may be used similarly, as long as a concentrate is producedwhich contains 80 to 95% aro matics, has an API gravity of about l7to 22 and boils predominantly in the 400 to 535 F. range, i.e., 'it may have an initial boiling point between about 300 and 400 F., and a final boiling point between about 525.

' and 625 F. Accordingly, the distillate to be extracted may be a wide-cut virgin naphtha fraction, a kerosene fraction or a light virgin gas oil, or it may be a virgin fraction including heavy naphtha, kerosene and light gas,

oil constitutents. The light ends, being predominantly "non-aromatic, tend to be automatically segregated from 235 and 600 F. was separated from Tomball crude. oil and extracted with sulfur dioxide in the usual manner.

the desired aromatic concentrate during the extraction.

7 EXAMPLE 1 As an example, a virgin distillate boiling between about The resulting aromatic extract orconcentrate was freed of solvent by distilling olf sulfur dioxide and was purified further by treatment with caustic and blown bright with I below.

Table I also lists the properties of a similar product s:(Extract B) Which was obtained by sulfur dioxide exkerosene of the type conventionally used as a base'for insecticidal compositions, Suchkerosene .is fayneutral, inert white oil which usually consists flessentially of alkylated cycloparafiins and a small amountof paraffins. It is commonly made by the action of fuming sulfuric acid ,on akerosene distillate fraction at about to 1 Table I PROPERTIES or VIRGINJXROMATIC EXTRACTS followed by neutralization with soda, washin with water, and filtration through adsorbent clay or the like.

The 50% blends were then used in accordance with the Peet Grady method (1954 Blue Book, Soap and San. Chem., pp. 243-4) in a comparative test on houseflies. The results obtained are summarized in Table I-A.

Table I-A COMPARATIVE ACTIVITY OF VIRGIN EXTRACTS Fly Knockdown (Percent) in.- Type of Aromatic Oil (50% in dcodorized kerosene) 2 min- 4 min- 6 min 8 min- 10 minutes utes utcs utes utcs Extract A 25 54- 85 93 96 Extract B 21 57 6G 81 86 The data show that both extracts were unusually effective in their insecticidal activity, but extract A which was derived from the aromatic Texas Gulf crude was especially outstanding.

EXAMPLE 2 The virgin extract A described in Example 1 above was further tested on houseflies by the Peet Grady method, this time in 100% concentration. In a comparative set of tests the virgin extract was found to be extremely rapid in its action, much more so than a similar catalytic cracked aromatic fraction or a catalytic reformed aromatic fraction.

The catalytic cracked aromatic fraction had the following properties:

API gravity 22.0 Flash (0. cup) F 178 Pour point F 10 Aniline point F 98.6 Total aromatics vol. percent 70 Init. B.P. T... 390 50% F 480 Final B.P. F 580 The catalytic reformed fraction had a total aromatics content of 93 vol. percent and an API gravity of 27.2.

The results of the bioassays run on the several fractions, in terms of percentage of housefiies knocked down after two minutes exposure, are summarized in Table H.

Table II COMPARATIVE KNOCKDOWN ACTIVITY OF CONCEN- TRATED OILS.

Type'of aromatic oil:

Virginaromatic extract A (invention) 83 Catalytic cracked fraction 55 Catalytic reformed fraction"..- 28' The data clearly demonstrates the great. insecticidal superiority of thevirgin extractover th'e non-virgin ma Fly knockdown, percent terials. Also, while a strict comparison between the results of Tables I and II is not justified due to the difference in atmospheric conditions aswell as a difference in flies used in the two separate sets of tests, the data of Table II nevertheless indicates the much greater potency of the concentrated material as compared with the dilute one. However, the virgin material constitutes a valuable insecticide even at high dilutions.

EXAMPLE 3 T able III COMPARISON WITH OFFICIAL TEST INSECIICIDE Fly Knockdown Type of Insecticide 4 min. 6 min. 8 min. 10 min.

Virgin Aromatic Extract A 65 93 Oflicial Test Insecticide 57 64 71 EXAMPLE 4 The aforementioned extract A has also proved to be remarkably effective in its kill of roaches (Blafella germanica). When used in concentration, extract A resulted in a roach kill of 22% compared to 27% with the Official Test Insecticide (O.T.I.) using the Official Cockroach Spray Method of the Chemical Specialties Manufacturers Association at a dosage of 0.5 cc. (Proceedings Chem. Spec. Manuf. Assoc., May 1953, pp. -112). This represents a truly outstanding result since heretofore no other all-petroleum product came anywhere near to the expensive O.T.I. composition in its effectiveness as a roach killer.

EXAMPLE 5 The great insecticidal effectiveness of the virgin extract in dilute form is apparent from the results in Table IV. This table shows the comparative effectiveness of the three fractions used in Example 2, but in this case after being diluted to 12.5 percent with a conventional deodorized flyspray kerosene base.

Table IV COMPARATIVE KNOCKDOWN ACTIVITY OF DILUTE OILS Fly Knockdown Type of Arfimatic Oil (12.5% in eroscne) 2 4 (i 8 10 min. min. min. min. min.

Virgin Aromatic Extract A 21 50 66 71 77 Catalytic Cracked Fraction- 19 33 4G 18 5Q Catalytic Reformed Fraction. 17 3O 32 32 3.;

acts as a solvent for various insecticidal materials such as the ones'listed in Table V. Consequently, these are especially useful in conjunction-with the virgin aromatic ere t;

- EMF.

Table V SOLUBILITY OF VARIOUS TOXIOANTS IN VIRGIN AROMATIO EXTRACT Solubility (percent) Toxicant at DDT 30 35 Lindane (Gamma isomer of benzene hexachloride of 99+% purity) 7 Benzene Hexaohlnrirle 20 Methoxychlor (1 1,1-trichloro-2,2-bis (p-methoxyphenyl) ethane) 2s 40 Pentachlorophenol 10 17 Chlordane (1,2,4,5,6,7,8,8-octachloro-2,3,3a,4,7,7ahexahydro-afl-methanoindane and related compounds) 75 75+ Toxaphene (chlorinated camphene having a chlorine content of 67 to 69 75 2,4D, isopropyl ester (isopropyl ester of dichlorophenoxyacetic acid) 60 60+ 2,4-D, N -capryl.ester (N-capryl ester of dichlorophenoxyacetic acid) 60 60+ 2,4,5-T, N-capryl ester (N -capry1 ester of trichlorophenoxyacetic acid) 50 60+ Other toxicants and synergists suitable for use in conjunction with the virgin aromatic extracts include pyrethrins, allethrin, cyclethrin, insecticidal thiocyanates, piperonyl butoxide, Sulfoxide (n-octyl sulfoxide of isosafrole and related compounds), Octacide (n-octylbicycloheptene), Strobane (polychlorides of camphene, pinene and related terpenes), Perthane (diethyl-diphenyl dichloroethane), Dieldrin (85% hexachloroepoxyoctahydro-dimethanonaphthalene and 15% related compounds), Heptachlor (1 or 3a,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methanoindene), Malathion (0,0-dimethyl dithiophosphate of diethyl mercaptosuccinate), etc.

Depending on the specific agents used, such toxicants and synergists, or various combinations thereof, may be included in the novel compositions in concentrations which may range from about 0.025 to weight percent, eg about 0.05 to 8%. For instance, pyrethrins, allethrims and the like are generally used in concentrations of 0.025 to about 0.5%, piperonyl butoxide and the like in the range of about 0.2 to 2%, thiocyanates in the range of about 0.5 to 3%, Strobane, Perthane and the like in the range of about 0.2 to 8%, and so forth. It will be understood that suitable concentrations are readily determined by those skilled in the art and that the foregoing figures have been listed here primarily for purposes of illustration rather than limitation.

EXAMPLE 6 Aerosols, which normally contain about 80 to 90 percent volatile propellant and 20 to 10 percent of nonvolatile ingredients, represent another valuable embodiment of the invention. Such an aerosol is illustrated by the following composition.

I Weight percent Virgin aromatic extract A (same as in previous Difluoro-dichloromethane 42.50

This composition was tested using the C.S.M.A.; Official Aerosol Test Method for Flying Insects (Proceedings, Chem. Specialties Manuf. Assoc., '1953, pp. 50 -53), and compared to the same formulation in which the aromatic fraction was replaced with deodorized kerosene. The data are summarized in Table VI.

6 Table VI AEROSOL TEST Flying Insect Knockdown,

percent Aerosol Composition 6 min. 10 min. 15 min.

With Virgin Aromatic Extract A 21 40 Without Virgin Aromatic Extract A 7 15 EXAMPLE 7 While aromatic extracts of the type illustrated above constitute very superiorinsecticidal materials, particularly outstanding results are obtained when only the higher boiling fractions of these extracts, i.e. particularly those boiling above about 460, or especially above 470 F. and below 535 F., are used. 7

To illustrate this, the virgin extract A described above was vacuum distilled and the higher boiling fraction representing approximately the 60 to 95 vol. percent portion was segrated for further evaluation. This fraction is hereafter designated as Fraction AA. While the uppermost 5% were also highly active they tended to contain some heavy material which had a tendency to cause un- Wanted stains and were therefore excluded.

Fraction AA, representing 35 vol. percent of the original virgin aromatic product, had the following charac teristics:

Initial boiling point F 464 Final boiling point F 532. Aromatics volume percent After dilution to a 20% concentration by blending with deodorized kerosene, the narrow cut aromatic fraction AA was tested by the Peet Grady method against a similar dilution of the extract A.

The bioassays of the two 20% blends are summarized in Table VII.

Table VII Fly Knockdown percent Active Ingredient (in 20% concentration) min. min. min. min.

Aromatic Extract A 16 27 40 50 54 68 76 61 Higher Boiling Fraction AA 31 87 7, Table VIII 'AOTIVITY ACCORDING TO BOILING RANGE Fly Knockdown, Percent Boiling Range of Active Fraction 2 min- 4 min- 6 min- 10 minutes utes utes utes The data, particularly in conjunction with those of Table VII, indicatethat the most active components are present in the fraction boiling between about 450 to 550 F., or especially in the fraction boiling above about .460 and below 500 F. Conversely, while the material boil- COMPARISON OF VIRGIN AND CATALYTIC OILS Fly Knockdown, Percent Type of Oil 2 min- 4 min- 6 minminutes utes utes utcs Fraction AA 23 36 49 64 Hydrolormed Fraction 9 20 28 42 The superiority of the virgin product over the catalytic one is again readily apparent. Tested undiluted against the Oflicial Test Insecticide, the higher boiling aromatic fraction AA produced a knockdown of 100% compared to 78% for the O.T.I. and a kill of 99% compared to 57% for the O.T.I. Thus the narrow-cut, heavy aromatic fraction by itself appears to far surpass the requirements for a Grade AA Liquid Insecticide (CCS 72-54, U.S. Dept. Com.) which requires a knockdown of .not less than 2 percentage points and a kill of +l6 percentage points compared to the Ofiicial Test Insecticide. The kill of this pure petroleum product is particularly astounding, as those skilled in the art will readily acknowledge; and this, combined with the outstanding knockdown activity, makes the aforementioned narrow-cut fraction a truly superlative insecticide.

The higher boiling aromatic fraction AA wasalso unusually eifective against roaches. Using the Official Roach Spray Method of the C.S.M.A., a kill of 97% was obtained compared to 100% with the O.T.I. Using the same method, the product was effective against other species of roaches, producing an 88% kill of male American roaches (Periplaneta americana) and a 100% kill of male oriental roaches (Blatta orientalis). Sinceroaches are notoriously difiicult to kill, the fact that the aromatic fraction AA substantially matches the excellent results obtained with the expensive O.T.I. composition represents convincing evidence of the excellence of the present invention.

The effectiveness of the aromatic fraction in a general purpose household insecticide was determined in the following formulation:

NEVV FORlliULA Weight percent DDT 3.0 Lindane 0.1 Thanite 0.5 Deodorized kerosene 71.4 Aromatic fraction AA 25.0

This formulation was compared with the following conventional commercial formulation:

OLD FORMULA Weight percent b-lhtocyanoethyl esters of mixed fatty acids averaging 10 to 18 carbon atoms (75%) and b-butoxyl-b'-thiocyanodiethyl ether (25%), diluted with an equal volume of deodorized kerosene.

Results of the tests are shown in Table X.

Table X Fly Knockdown, Percent Formulations 2min- 4rm'n- 6min- 8min- 10minutcs utes utes utcs utes Invention 46 66 77 92 96 Old Formula 45 63 77 86 93 These data indicate that the aromatic fraction can replace expensive knockdown agents such as allethrin, piperonyl butoxide and Lethane 384 Special. In fact a Grade AA household insecticide with residual effect can be prepared as follows:

Weight percent 5 DDT Aromatic fraction AA 13 Base oil 82 The aromatic fraction is also applicable for use in pressurized formulations. For instance, an excellent roach aerosol spray can be prepared as follows:

The aromatic fraction also possesses insecticide action against pests affecting crops. It may be applied as a fog when used in a fog generator. More permanent insecticide formulations preferably include compounding of the aromatic fraction with other toxicants such as DDT, methoxychlor, Toxaphene, benzene hexachloride, aldrin, Parathion, and similar substances. As is apparent from the formulas shown in Example 6 and in Formula .W below, DDT for instance may constitute about 2 to 25% of the novel compositions.

The aromatic fraction can also be applied in the form of an emulsion. A concentrate can be formulated consisting of the aromatic fraction and a conventional emulsifying agent, such as alkyl lauryl polyethylene alcohol, alkyl polyoxyethylene glycol ester, and polyoxyethylene sorbitol oleate. This is added to water and applied to the crops or to livestock by means of conventional spray equipment. Residual action may be obtained by combining the aromatic fraction with a toxicant such as those indicated above and a suitable emulsifying agent. This type of concentrate could consist ofthe following ma terials:

FORMULA W Weight percent DDT 25 Polyoxyethylene sorbitol oleate 5 Aromatic fraction AA 70 clusion of unspecified materials such as diluents, propellants, auxiliary toxicants or synergists which do not alfect the basic character of the composition claimed.

What is claimed is:

1. A pesticidal concentrate consisting essentially of a highly aromatic extract of a virgin distillate of a Texas Gulf crude oil, said extract boiling in the range of about 400 to 535 F. and having a total aromatics content of 80 to 95 volume percent.

2. A pesticidal composition the active ingredient of which consists essentially of a highly aromatic sulfur dioxide extract of a virgin distillate of Tomball crude oil, said virgin extract having a boiling range of about 450 to 535 F. and a total aromatics content of about 80 to 95 volume percent.

3. A pesticidal spray composition consisting essentially of a highly aromatic extract of a Texas Gulf virgin petroleum distillate in combination with a minor amount of a chemical toxicant, said aromatic extract boiling predominantly in the range of about 400 to 535 F. and having a total aromatics content of 80 to 95 volume percent.

4. A pesticidal spray composition according to claim 3 wherein the aromatic extract is derived from Tomball crude and has a boiling range of about 450 to 535 F.

5. A pesticidal aerosol composition consisting essentially of a highly aromatic extract of a virgin Texas Gulf petroleum distillate in combination with a major amount of a liquefied halogenated C -C alkane propellant and a minor amount of a chemical toxicant, said extract boiling predominantly in the range of about 400 to 535 F. and having an aromatics content of 80 to 95 volume percent.

6. A pressurized pesticide spray composition consisting essentially of a highly aromatic sulfur dioxide extract of a virgin Tomball crude distillate in combination with a minor amount of a chemical toxicant, a refined essentially inert kerosene base oil, and sufficient liquefied gas to produce a suitable spray pattern, said extract having a boiling range predominantly between about 450 to 535 F. and a total aromatics content of 80 to 95 volume percent.

7. A pesticidal emulsion concentrate consisting essentially of a highly aromatic extract of a virgin Texas Gulf distillate in combination with a minor amount of an emulsifying agent, said extract boiling predominantly in the range of about 400 to 535 F.

8. A pesticidal concentrate according to claim 7 wherein the extract is derived from Tomball crude and has a boiling range of about 460 to 535 F.

9. A pesticide emulsion concentrate according to claim 8, in further combination with a minor amount of a chemical toxicant.

10. A pesticidal fog concentrate consisting essentially of a sulfur dioxide extract of a virgin Texas Gulf distillate in combination with a minor amount of a chlorinated aromatic hydrocarbon toxicant, said extract having a boiling range of about 460 to 535 F. and a total aromatics content of 80 to 95 volume percent.

11. An insecticidal composition consisting of 10 to 30 percent of a sulfur dioxide extract of a virgin Texas Gulf distillate, 90 to percent of a refined essentially inert kerosene base oil, and 0 to 25 percent of a chlorinated aromatic hydrocarbon toxicant, said extract having a boiling range of about 460 to 535 F. and a total aromatics content of about 85 to 95 volume percent.

12. An insecticidal composition according to claim 11 wherein the chlorinated toxicant is dichlorodiphenyl trichloroethane present in a conentration of from 2 to 25 percent.

13. A process for killing insects which comprises applying to such insects an aromatic extract of a virgin petroleum distillate, said extract being derived from Texas Gulf crude oil and boiling in the range of about 400 to 535 F. and containing to 95 volume percent of aromatics.

14. A process according to claim 13 wherein the extract is a sulfur dioxide extract derived from Tomball crude oil and having a boiling range predominantly between about 460 and 535 F.

15. A process according to claim 14 wherein the extract is used in combination with a minor amount of a chlorinated aromatic hydrocarbon toxicant.

16. A process of killing insects which comprises applying to such insects an insecticide consisting of an aromatic sulfur dioxide extract of a virgin distillate of a Tomball crude oil, said extract having a boiling range of about 460 to 535 F. and a total aromatics content of to volume percent.

17. A process according to claim 16 wherein the insects are houseflies.

18. A process according to claim 16 wherein the insects are roaches.

19. An enclosure containing a pesticidal aerosol composition consisting essentially of a highly aromatic extract of a virgin distillate of Tomball crude oil in combination with a major amount of a liquefied halogenated C -C alkane propellant and a minor amount of an extraneous chemical toxicant, said extract boiling predominantly in the range of about 450 to 535 F. and having an aromatics content of 80 to 95 volume percent.

References Cited in the file of this patent UNITED STATES PATENTS 

16. A PROCESS OF KILLING INSECTS WHICH COMPRISES APPLYING TO SUCH INSECTS AN INSECTICIDE CONSISTING OF AN AROMATIC SULFUR DIOXIDE EXTRACT OF A VIRGIN DISTILLATE OF A TOMBALL CRUDE OIL, SAID EXTRACT HAVING A BOILING RANGE OF ABOUT 460 TO 535*F., AND A TOTAL AROMATICS CONTENT OF 85 TO 95 VOLUME PERCENT. 